Adsorption of CO on a Platinum (111) surface - a study within a four-component relativistic density functional approach

We report on results of a theoretical study of the adsorption process of a single carbon oxide molecule on a Platinum (111) surface. A four-component relativistic density functional method was applied to account for a proper description of the strong relativistic effects. A limited number of atoms in the framework of a cluster approach is used to describe the surface. Different adsorption sites are investigated. We found that CO is preferably adsorbed at the top position.Comment: 23 Pages with 4 figure

Orbital optimization in the perfect pairing hierarchy. Applications to full-valence calculations on linear polyacenes

We describe the implementation of orbital optimization for the models in the perfect pairing hierarchy [Lehtola et al, J. Chem. Phys. 145, 134110 (2016)]. Orbital optimization, which is generally necessary to obtain reliable results, is pursued at perfect pairing (PP) and perfect quadruples (PQ) levels of theory for applications on linear polyacenes, which are believed to exhibit strong correlation in the {\pi} space. While local minima and {\sigma}-{\pi} symmetry breaking solutions were found for PP orbitals, no such problems were encountered for PQ orbitals. The PQ orbitals are used for single-point calculations at PP, PQ and perfect hextuples (PH) levels of theory, both only in the {\pi} subspace, as well as in the full {\sigma}{\pi} valence space. It is numerically demonstrated that the inclusion of single excitations is necessary also when optimized orbitals are used. PH is found to yield good agreement with previously published density matrix renormalization group (DMRG) data in the {\pi} space, capturing over 95% of the correlation energy. Full-valence calculations made possible by our novel, efficient code reveal that strong correlations are weaker when larger bases or active spaces are employed than in previous calculations. The largest full-valence PH calculations presented correspond to a (192e,192o) problem.Comment: 19 pages, 4 figure

Electronic Excitations in Complex Molecular Environments: Many-Body Green's Functions Theory in VOTCA-XTP

Many-body Green's functions theory within the GW approximation and the Bethe-Salpeter Equation (BSE) is implemented in the open-source VOTCA-XTP software, aiming at the calculation of electronically excited states in complex molecular environments. Based on Gaussian-type atomic orbitals and making use of resolution of identify techniques, the code is designed specifically for non-periodic systems. Application to the small molecule reference set successfully validates the methodology and its implementation for a variety of excitation types covering an energy range from 2-8 eV in single molecules. Further, embedding each GW-BSE calculation into an atomistically resolved surrounding, typically obtained from Molecular Dynamics, accounts for effects originating from local fields and polarization. Using aqueous DNA as a prototypical system, different levels of electrostatic coupling between the regions in this GW-BSE/MM setup are demonstrated. Particular attention is paid to charge-transfer (CT) excitations in adenine base pairs. It is found that their energy is extremely sensitive to the specific environment and to polarization effects. The calculated redshift of the CT excitation energy compared to a nucelobase dimer treated in vacuum is of the order of 1 eV, which matches expectations from experimental data. Predicted lowest CT energies are below that of a single nucleobase excitation, indicating the possibility of an initial (fast) decay of such an UV excited state into a bi-nucleobase CT exciton. The results show that VOTCA-XTP's GW-BSE/MM is a powerful tool to study a wide range of types of electronic excitations in complex molecular environments

Multi-component symmetry-projected approach for molecular ground state correlations

The symmetry-projected Hartree--Fock ansatz for the electronic structure problem can efficiently account for static correlation in molecules, yet it is often unable to describe dynamic correlation in a balanced manner. Here, we consider a multi-component, systematically-improvable approach, that accounts for all ground state correlations. Our approach is based on linear combinations of symmetry-projected configurations built out of a set of non-orthogonal, variationally optimized determinants. The resulting wavefunction preserves the symmetries of the original Hamiltonian even though it is written as a superposition of deformed (broken-symmetry) determinants. We show how short expansions of this kind can provide a very accurate description of the electronic structure of simple chemical systems such as the nitrogen and the water molecules, along the entire dissociation profile. In addition, we apply this multi-component symmetry-projected approach to provide an accurate interconversion profile among the peroxo and bis($\mu$-oxo) forms of [Cu$_2$O$_2$]$^{2+}$, comparable to other state-of-the-art quantum chemical methods

Calculating Hyperfine Couplings in Large Ionic Crystals Containing Hundreds of QM Atoms: Subsystem DFT is the Key

We present an application of the linear scaling Frozen Density Embedding (FDE) formulation of subsystem DFT to the calculation of isotropic hyperfine coupling constants (hfccs) of atoms belonging to a guanine radical cation embedded in a guanine hydrochloride monohydrate crystal. The model systems considered range from an isolated guanine to a 15,000 atom QM/MM cluster where the QM region is comprised of 36 protonated guanine cations, 36 chlorine anions and 42 water molecules. Our calculations show that the embedding effects of the surrounding crystal cannot be reproduced neither by small model systems nor by a pure QM/MM procedure. Instead, a large QM region is needed to fully capture the complicated nature of the embedding effects in this system. The unprecedented system size for a relativistic all-electron isotropic hfccs calculation can be approached in this work because the local nature of the electronic structure of the organic crystals considered is fully captured by the FDE approach